Azo dyestuffs insoluble in water and fiber dyed therewith



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Patented June 20, 1939 OFFICE AZO DYESTUFF'S INSOLUBLE IN WATER AND FIBER DYEDHTHEREWITH Erwin Thoma, Frankfort-on-the-Main-Hochst,

and Wilhelm Seidenfaden, Offenbach-on-the- Main, Germany, assignors to General Aniline Works, Inc., New York,- N. Y., a corporation of Delaware No Drawing. Application March 23, 1937, Serial No. 132,632. In Germany April 2, 1936 10 Claims.

The present invention relates to 'azo-dyestufis insoluble in water and to fiber dyed therewith, more particularly it relates to'dyestuffs of the following general formula:

OH RN=NRiN=N-R2 X C O-NH-Ra wherein the azo-groups standin para-position to each other, R, R1 and R3 stand for radicals of the benzene or naphthalene series, Rzstands for a radical of the naphthalene series and X for a a member of the group consisting of --CO.alkyl,

1k 1 1k 1 /a y a y N\ and N SOaalkyl SOaCsHs We have found that valuable water-insoluble azo-dyestufis are obtainable by coupling an arylbeta-ketocarboxylic acid with a diazo-compound of a para-aminoazo-compound of the benzene or naphthalene series which contains as a sub-' stituent at least one group containing the radi-' cal: VCO or S02 which on the one hand is connected with a hydrocarbon radical directly or through an oxygen bridge or through a nitrogen bridge having as a substituent at the third bond a hydrocarbon, radical; and on the other hand is connected with the benzene or naphtha-" 7 ide of an ortho-hydroxyarylcarboxylic acid or (o1. zoo-18s) lene radical of the para-aminoazo-compound directly or through. an oxygen bridge and/or through a hydrocarbon bridge or through a nitrogen bridge containing as a substituent at the third bond a hydrocarbon radical; the dyestuff components must not contain any group which lends solubility, for instance a sulfonic acid or carboxylic acid group. The dyestuffs may be made in substance, on a fiber or on a substratum adapted for the production of lakes.

.The para-aminoazo-compounds of the benzene or naphthalene series used as diazo-components may contain substituents of the following kind:- .CO.alkyl, -CO-C6H5, CH=CH.CO.C6H5,

O.CH2.C0.alkyl, -O.CH2.CO.C6H5,

CH2. C5115 CO.C5H5

alkyl alkyl The diazonium compounds, for example the diazonium chlorides and the zinc-chloride double salts'of these chlorides are in part easily soluble so that in making the dyestuffs in substance no large dilution is necessary, and in producing the dyestuff on the fiber in printing a material concentrated printing pastes are obtainable. In producing the dyestuff on yarn there may be alkyl and N added to the diazo-salt solution a salt, as is the Furthermore, in the case of the diazproperty makes it possible, after the production of the dyestufi, to wash out easily non-coupled portions of diazonium salt. Many combinations do not bleed yellow in the washing sample and thus do not show a defect which is frequently to be observed in the combinations from diazotized 4-aminoazo-compounds which are frequently used in practice. Other combinations are of high fastness to light.

The new dyestuffs are of very various tints. Thus, by using arylides of beta-ketocarboxylic acids, there are obtained on the fiber orangeyellow, orange-red, orange-brown, scarlet, bluishred, bordeauX-red and brown-red tints which in part cannot be obtained with the already known para-aminoazo-compounds. With the arylides of ortho hydroxy carbazole. carboxylic acids there may be obtained for example, currant tints of high fastness to light. Further, fine black tints are obtained which in part are essentially faster to light than the dyeings obtainable from 1 known paraaminoaZo-compounds. By using 2,3-

hydroxynaphthoic acid-arylides, there are obtained, for example bordeaux, currant, garnet, navy blue and greenish-blue, blue-black, blackviolet and deep grey tints which in many cases are distinguished by a high fastness to light and good fastness to washing and chlorine.

The color tints are profoundly dependent, apart from the kind of coupling component, on the kind of the aforesaid substituents and on the position which they have in the para-aminoazo body of the benzene or naphthalene series. Further, the presence of other substituents such as alkyl-, alkoxyor nitro-groups and halogen is of importance.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto: I

1. 50 grams of cotton yarn are treated with 1 liter of an alkaline grounding solution which contains 2.5 grams of the arylide of the following constitution:

2'-carboxylic acid diethylamide-4-aminoazobene zene,there is also obtained a black of very good fastness to light;

' If for developing the dyestuif there is used a diazo-solution from 4-grams of 2,5-2'-trimethoxy-5-carboxylic acid-diethylamide 4 amino-.

azobenzene made by diazotizing the base in 4 cc.

of hydrochloric acid of 30 per cent. strength and water by means of 0.7 gram of sodium nitrite and making up the solution to 1 liter by addition of 40 grams of sodium chloride, 4 grams of sodium acetate and 0.7 gram of sodium bicarbonate, there is obtained a black fast to light.

7 methoxy-3,4' -bis- (carboxylic If the diazo-compound from 4-amino-2-methoxy-5-methyl-4'carboxylic acid-diethyl-amideazobenzene or from 4 amino 2 methoxy 5 methyl-2-carboxylic acid-diethylamide-azoben zene is used there is also obtained a valuable black.

By using as coupling component an arylide of the following constitution:

own-O0 on;

there are obtained valuable black tints with the diazo-compounds from: 4-amino-2,5-dimethoxy 4 N methylphenylsulfonylaminoazobenzene, 4- amino-S- methoxy 3 oarboxylic acid diethylamide-azobenzene, or 4-amino-2,5-dimethoxy-2- phenylsulfonylmethyl-azobenzene.

2. 50 grams of cotton yarn are treated in one liter of an alkaline grounding solution which contains 1.8 grams of 1-(2-hydroxy-3-carbazole carbonylamino) 4 ohlorobenzene. T h e grounded yarn is developed with a solution of 4 grams of the zinc-chloride double salt of 2,5- dimethoxy- 3' acetylazobenzene 4 diazoniumchloride, 0.6 gram of glacial acetic acid and. 20 grams of sodium sulfate per liter. After soaping with 3 grams of soap and 1 gram of sodium carbonate per liter, there is obtained a violetbrown fast to light.

If the development is conducted with a diazosolution from 3.6 grams of 2,5dimethoXy- 2-carboxylio acid-diethylamide-4-aminoazobenzene, a violet of good fastness to light is obtained. By using the 2-methyl methoxy 4 carboxylic acid-diethylamidel-aminoazobenzene as the diazo-component, a. currant tint is obtained. With the diazo-compounds from 4-amino-2,5-dimethoxy-2'-carboxylic acid-diethylamide azobenzene or from 4 amino 2,5 diethoxy -4' phenylsulfonylmethyl-azobenzene there are obtained covered violet tints.

3. A mercerised calico is grounded with a padding solution which contains per liter 15 grams of 4,4-di- (aceto-acetylamino) -3,3-dimethyldiphenyl. It is then printed with a diazo solution from 18 grams of 2,5-dimethoxy-2,5-bis-(carboxylicacid-diethylamide)-4-aminoazobenzene, 14 cc. of hydrochloric acid of 30 per cent. strength, 3 grams of sodium nitrite and 6 grams of sodium acetate, the whole havingbeen made up to 500 cc. and then made up to 1 liter by addition of a thickening agent. After drying, the material is handled in a solution of 10 grams of sodium carbonate per liter at 90 C., rinsed, soaped at the boil and rinsed. There is obtained a scarlet-red.

When one uses as diazo-component 4-amino- 2,5-dimethoxy-4'-acetylazobenzene, there is obtained a medium red; with 4-amino-2,5-diacid-ethylester) azobenzene, there is also obtained a middle red; with 4-amino-2,5-diethoxy-2'ecarboxylic acidethylester-4'-nitro-azobenzene, there is obtained a dark red-brown; with 4-amino-2,5-dimethoxy- 2-methylsulfonyl-4-nitro-azobenzene, there is on a foulard in a solution which contains per liter 1 (2",3' hydro-xynaphthoylamino) benzene i grams" 15 Caustic soda solution of 34 B oc 22.5. Turkey-red oil cc 15 and dried. On the goods thus grounded the-re is printed a paste which contains 2,5 dimethoxy 4 nitro azobenzene- 2' carboxylic acid ethylester 4 diaZonium-chloride grams 20 Acetic acid of 50 per cent strength do 50 Water do 430 Starch tragacanth thickening do 500 Grams" 1000 After drying the material is passed through a hot sodium carbonate solution (containing 2 grams of anhydrous sodium carbonate per liter) and soaped at boiling temperature. There is obtained a deep black of very good fastness to light.

The dyestuff corresponds With the following formula:

OCH:

| C OO.C2H5 CH2 Diazo component Coupling component Shade 1-(2. 3-hydroxynaphthoylarnino) 4-a1n1no-2-carboxyl1c acld-drethylamide-ie'nethoxyazobenzene -benzene Bordeaux.

4-agnino-2-earboxylic ocid-diethylamide-2-n1etl1yl-4-methoxyazoenzene.

-i-amino-2-N-pl1enylsulfony1-1n ethylamine-5-meth0xy 4- n i t r o a z 0 benzene.

'l-amino-3-meth oxy-3-carboxylic acid diethylomide-azobenzene...

Do 4-amino-2-1nethyl-5-u1ethoxy-3-carboxylic acid (liethylamideazobenzene. 4-amino-Z-methoxy-5-methyl-2-corboxylie acid-diethylarnideazoncid-diethyl amide-azabenzene. 4-amino-2-methoXy-5-methyl-5-carhox3- lie benzene. 4-arnino-2-methcxy-5-mothyl4-carboxylic acid-diethylamide-szobenzene.

Do Do- 4-amino-2, 5-dimcthoxy-2-acetyl-azobenzene. 4-amino-2, 5-dirnethoxy-3-acetyl-azobenzene 4-emino-2, 5-dimethoxy-4'-acetyl-azobenzene 4-amino-2, 5-diinethoxy-4-acetyl-2-methoxy-azobenzene 4-emino-2, 5-diInethoxy-4-benzoyl-azobenzene 4-amino-2, 5-dimethoxy-2-corboxylie acid methylester-azobenzene 4-amino-2, 5-dimethoxy-4-carboxylic acid-ethylestenazobenzene.-- 4-an1ino-2 5-dimethoxy-2-carboxylic acid-diet]:ylamide-azobenzene..

etho arboxylic acid-diethylamide-azobenzene 4-amino-2,5-diu1eth0xy-4-carboxylic acid-dictliylamide-o zobenzene 4-aminc-2,5-dimethoxy3-carboxylic acid-Ner-ethylanilide-ozobenzene.

4-211?inc-2,5-dimethoxy-2,5-bis-(cerbcxylic acid-diethylamide)-azocnzene. I

4-aminc-2,5-dimethoxy-'Z-carboxylie acid-piperidide-4-nitro-az0benzene. 4-amino-2, 5-dimcthoxy-3-N-phenylsulfonylmethylamine-azobenzene. 4-emino-2, 5-dimethoxy-2-N-phenylsulfonyl-methylamine-5-1neth oxy-azo-benzene.

4-amino-2, 5-dimeth0xy-3-N-phenyl-sulfony1methylamine-4-n1ethoxy-azobenzene.

4-amino-2, 5-dimethoxy-3-N-phenyl-sulionylmethylamine-G-methoxy-azobenzene.

4-amino-2, 5-di1nethoxy-4-N-phenylsulfony1methylamine-3'-rnethoxy-azobenzene.

4-amino-2, fi-dimethoxy4'-N-phenylsulfonyl-methylarcine-azoben-- -2, fi-dimethoxybenzene Do.

-2-1nethyl-4-methoxybenzene Very deep current.

-2, 5-din1etl1oxy-4-chlorobenzene Dark current.

Currant.

o. Dull currant. Deep current. Redgish dull blue.

Blue-black. Very reddish dull blue.

-2, i-dimethoxybenzene -2, lf-1dimethoxy-5-chlorobenzene fl -4-methoxybenzene -2, fi-dimethoxybenzene -2-methyl-4-chlorobenzene -2, 4-dimethoXy-5-chlorobenzene -4-ehlorobenzene -2-methylbenzene Dull blue. -4-chlorobenzene Blue-black.

-2, 4-dimethoxy-5-chlorobenzene Reddish dark blue. -4-methoxybenzene Very reddish dark blue. -2,4-dimethoxy-5-chlorobenzene Reddish blue-black. -2,fi-dimethoxyi-chlorobenzene Very reddish blue.

-benzene Reddish blue.

do Greenish dull blue.

-2-methylbenzene Black. -3-methyl-4-methoxy-benzene.-. Dov -2-n1ethyl-4-meLh0xy-benzene Dark blue. -2,5-dimethoxy-4-chlorobenzene. Do. naphthalene Blue-black. benzene. Deep blue.

.... .do Blacl;violet. -2.4-dirnet Do. -2-methyl-4-chlorobenzene Dull blue.

do Black-violet.

-2,4-dimethoxy-fi-chlorobenzene Blue-black.

-benzene Very reddish dark blue.

-2, fi-dimethoxyl-chlorobenzene Dark blue.

-4-ehlorobenzene Blue-black.

2, 4-dimethoxy-5-chlorobenzene Do.

-2-methyl-4-ch1orobenzene Do.

2 (2,3-hydroxynaphthoylamino)- -naphthalene .Black.

wherein the azo-groups stand in para-position to (39h other, R, R1 and R3 stand for members of the group consisting of radicals of the benzene and naphthalene series R2 stands for a radical of the naphthalene series and X for a member of the group consisting of: CO.alkyl, -CO.C6H5, -CH=CH.CO.C6H5, O.CI-Iz.CO.alkyl,

-O.CH2.CO.C6H5.

O.C.alky], -O.O.CaH5 (i i COO.alkyl, COO.C6H5,CH2.COO.alkyl,

-CH=CH.COO.a1kyl,

yielding, when produced on the fiber, garnet to black dyeings of good fastness properties.

2. The water-insoluble azo-dyestuifs of the following general formula:

RN=NR;NN X/ I OH wherein the azo-groups stand in para-position to each other, R, R1 and R3 stand for radicals of the benzene series and X stands for a member of the group consisting of CO.alkyl, CO.CeH5. CH=CH.CO.CsH5, O.CI-I2.CO.alkyl,

O.CH2.CO.C6H5,

-COO.alkyl, COO.CsH5, CH2.COO.alky1,

-CH=CH.COO.alkyl,

alkyl alkyl S0z.alky1 50113 yielding, when produced on the fiber, garnet to black dyeings of good fastness properties. i

3. The water-insoluble azo-dyestuff of the following formula:

and N yielding, when produced on the fiber, a deep black dyeing of very good fastness to light, chlorine and ironing.

4. The water-insoluble azo-dyestufi of the following formula:

OOH:

CHaO

OOH;

yielding, when produced on the fiber, a blue-black dyeing of very good fastness to light and to chlorme.

5. Fiber dyed with the water-insoluble azodyestuffs as claimed in claim 1.

6. Fiber dyed with the water-insoluble azodyestuffs as claimed in claim 2.

'7. Fiber dyed with the water-insoluble azodyestufi as claimed in claim 3.

8. Fiber dyed with the water-insoluble azo-dyestuff as claimed in claim 4.

9. The water-insoluble azo-dyestuff of the following formula:

CH3 O N N=N- N yielding, when produced on the fiber, a blackblue dyeing of very good fastness to light and to chlorine.

10. Fiber dyed with the water-insoluble azodyestuff as claimed in claim 9.

ERWIN THOMA. WILHELM SEIDENFADEN. 

